CN107826462A - Extrusion coating paper of the laminated film containing stalk fibre and preparation method thereof - Google Patents

Extrusion coating paper of the laminated film containing stalk fibre and preparation method thereof Download PDF

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Publication number
CN107826462A
CN107826462A CN201711142841.6A CN201711142841A CN107826462A CN 107826462 A CN107826462 A CN 107826462A CN 201711142841 A CN201711142841 A CN 201711142841A CN 107826462 A CN107826462 A CN 107826462A
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stalk
preparation
parts
laminated film
hypochlorite
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Inventor
钱万水
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Wuhu Blue Sky Project Plastic Cement Co Ltd
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Wuhu Blue Sky Project Plastic Cement Co Ltd
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Priority to CN201711142841.6A priority Critical patent/CN107826462A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2497/00—Characterised by the use of lignin-containing materials
    • C08J2497/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/324—Alkali metal phosphate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/092—Polycarboxylic acids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Abstract

The invention discloses a kind of preparation method of the extrusion coating paper of laminated film containing stalk fibre, the preparation method includes：(1) stalk is crushed, be dispersed in water, oxidation processes are carried out in the presence of TEMPO (the piperidines N epoxides of 2,2,6,6 tetramethyl 1), hypochlorite, dried；(2) dried oxidation stalk, polyacrylate and organic solvent are mixed, is softened afterwards, obtain stalk mixture；(3) stalk mixture, polypropylene, citric acid, sodium dihydrogen phosphate, Tissuemat E, HBB and ethylene glycol are mixed, then carries out precompressed, hot pressing and sanding, film is made；(4) film is heated and hot pressing not only has good tensile strength in the extrusion coating paper that the laminated film containing stalk fibre has been made on the surface of paper layer, the laminated film, also with good gas permeability, be highly suitable for preparing the packaging material of fruits and vegetables.

Description

Extrusion coating paper of the laminated film containing stalk fibre and preparation method thereof
Technical field
The present invention relates to the preparation field of stalk material, in particular it relates to which a kind of laminated film containing stalk fibre is compound Paper and preparation method thereof.
Background technology
Any packaging material includes plastic sheeting or edible film, and oxygen, nitrogen, carbon dioxide and water are steamed The permeability measure of gas is particularly significant, and the packaging material particularly for preserving fruit and vegetable utilizing, its gas permeability is extremely important, because Film with Suitable breathable, the physiological metabolism after fruits and vegetables could be obtained and play certain regulating and controlling effect, so as to improve fruit The edible quality of vegetable, the frame goods life-span for extending fruits and vegetables, on the other hand, in order to obtain the material with fine air permeability, people are carried out Extensive research.
Chinese patent application 201110203184.8 discloses composition and its preparation side of a kind of low Air permenbility ventilated membrane Method, its component include：Polyolefin resin mixture, Air permenbility conditioning agent, surface be modified micro inorganic particle, antioxidant, Lubricant and coupling agent.It the advantage is that the mechanical property of ventilated membrane can be improved by receiving micron inorganic filler, while surface is coupled Modified inorganic particulate adds the compatibility with polyolefin base resin, but is disadvantageous in that high addition (30%- 55%) micron inorganic particulate can not be dispersed in matrix resin well, so as to have impact on the ventilative of thin-film material Uniformity.
Chinese patent application 201110125458.6 discloses a kind of polyolefin film and preparation method thereof, its component bag Include：Vistanex, pore former and extractant.It the advantage is that the structure of polypropylene/olefin film prepared by used conventional wet It is small, quantity is more, but it uses the extraction process of two step high volume percentage concentration, and its extractant is N, N '-dimethyl formyl Amine, dichloromethane, chloroform etc. belong to high pollution, toxic solvent, can cause huge injury to human body and environment.
Chinese patent application 201710110501.9 discloses a kind of gas permeability laminated film and preparation method thereof, and this is compound Film is prepared by the component of following percentage by weight：60%-82% vistanex polymer, 2%-8% is micro-nano Crystalline cellulose particle, 0.4%-1% antioxidant, 15%-30% dispersants, 0.1%-0.5% lubricants, 0.2%-1% couplings Agent.Its preparation method is as follows：Micro nanocrystalline cellulose aqueous dispersions and coupling agent are uniformly dispersed；It is equal to add dispersant Even and dry pretreated filler；Resulting pretreated filler, vistanex, antioxidant, lubricant are added to double spiral shells In bar extruder, by melting extrusion, cooling and gas permeability laminated film constituent is granulated to obtain, hot calender prepares flat film； Immerse in cleaning agent, ultrasound, dry again；Biaxial tension simultaneously carries out thermal finalization processing, obtains gas permeability laminated film.The laminated film Permeability is efficient, good mechanical performance.Shortcoming is to need to immerse in cleaning agent, and processing procedure is cumbersome.
Rationally, efficiently using agricultural straw resource, turn waste into wealth, production environment friendly materials turn into the world focus Problem.China is a large agricultural country, and rice, wheat, corn, cotton etc. is main variety of crops.China's crops straw Stalk annual production arranges No. 1 in the world up to 700,000,000 tons.At present, these agricultural crop straws rich in cellulose mainly have following processing side Formula, but all Shortcomings：1st, the waste treatment such as landfill, burning, not only without efficent use of resources, and in combustion can Substantial amounts of carbon dioxide is discharged, pollutes environment；2nd, preparing fuel ethanol, conversion ratio is low, and cost is high；3rd, combustion power generation, added value are low. Therefore, stalk efficiently also needed to using problem it is widely studied.Using original of the stalk as some laminated films such as density board Material, can not only turn waste into wealth, and can efficent use of resources, currently with stalk be laminated film made from raw material also deposit Mechanical strength is relatively low the problem of, but the tensile strength of stalk compound material is often improved, its gas permeability is undesirable, no It can realize and be used as vegetable and fruit packaging materials'use.
Therefore it provides a kind of mechanical strength is higher, while stalk fibre laminated film of good permeability and preparation method thereof The problem of being urgent need to resolve of the present invention.
The content of the invention
It is an object of the invention to provide extrusion coating paper of a kind of laminated film containing stalk fibre and preparation method thereof, solves mesh It is prepared by preceding the problem of overcoming mechanical strength and incompatible gas permeability using stalk for laminated film made from raw material, the present invention The laminated film containing stalk fibre extrusion coating paper in laminated film not only there is preferable tensile strength, also have good saturating Gas, and preparation method is simple, it is easy to accomplish.
To achieve these goals, the invention provides a kind of preparation side of the extrusion coating paper of laminated film containing stalk fibre Method, the preparation method include：(1) stalk is crushed, be dispersed in water, in TEMPO (2,2,6,6- tetramethyl -1- piperidines-N- Epoxide), carry out oxidation processes in the presence of hypochlorite, dry；(2) by dried oxidation stalk, polyacrylate Mixed with organic solvent, softened afterwards, obtain stalk mixture；(3) by stalk mixture, polypropylene, citric acid, Sodium dihydrogen phosphate, Tissuemat E, HBB and ethylene glycol mixing, then carry out precompressed, hot pressing and sanding, film are made；(4) will Film heat and hot pressing is on the surface of paper layer.
Present invention also offers a kind of extrusion coating paper of laminated film containing stalk fibre, the laminated film containing stalk fibre Extrusion coating paper is made by above-mentioned preparation method.
Pass through above-mentioned technical proposal, the invention provides a kind of extrusion coating paper of laminated film containing stalk fibre and its preparation side Method, the preparation method include：(1) stalk is crushed, be dispersed in water, in TEMPO (2,2,6,6- tetramethyl -1- piperidines-N- Epoxide), carry out oxidation processes in the presence of hypochlorite, dry；(2) by dried oxidation stalk, polyacrylate Mixed with organic solvent, softened afterwards, obtain stalk mixture；(3) by stalk mixture, polypropylene, citric acid, Sodium dihydrogen phosphate, Tissuemat E, HBB and ethylene glycol mixing, then carry out precompressed, hot pressing and sanding, film are made；(4) will Film heat and hot pressing is on the surface of paper layer.I.e. by the way that stalk to be aoxidized to, softened and prepared poly- the third of laminated film Alkenyl body mixes, and stalk fibre laminated film has been made, and the laminated film not only has good tensile strength, also has good Gas permeability, film heat and hot pressing is in being made Film laminated paper on the surface of paper layer, is highly suitable for preparing fruit The packaging material of vegetable.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more New number range, these number ranges should be considered as specific open herein.
The invention provides a kind of preparation method of the extrusion coating paper of laminated film containing stalk fibre, the preparation method bag Include：(1) stalk is crushed, be dispersed in water, deposited in TEMPO (2,2,6,6- tetramethyl -1- piperidines-N- epoxides), hypochlorite Oxidation processes are carried out in case, are dried；(2) dried oxidation stalk, polyacrylate and organic solvent are mixed Close, softened afterwards, obtain stalk mixture；(3) by stalk mixture, polypropylene, citric acid, sodium dihydrogen phosphate, poly- second Alkene wax, HBB and ethylene glycol mixing, then carry out precompressed, hot pressing and sanding, film are made；(4) film is heated simultaneously Hot pressing is on the surface of paper layer.
Pass through above-mentioned technical proposal, the invention provides a kind of extrusion coating paper of laminated film containing stalk fibre and its preparation side Method, the preparation method include：(1) stalk is crushed, be dispersed in water, in TEMPO (2,2,6,6- tetramethyl -1- piperidines-N- Epoxide), carry out oxidation processes in the presence of hypochlorite, dry；(2) by dried oxidation stalk, polyacrylate Mixed with organic solvent, softened afterwards, obtain stalk mixture；(3) by stalk mixture, polypropylene, citric acid, Sodium dihydrogen phosphate, Tissuemat E, HBB and ethylene glycol mixing, then carry out precompressed, hot pressing and sanding, film are made；(4) will Film heat and hot pressing is on the surface of paper layer.I.e. by the way that stalk to be aoxidized to, softened and prepared poly- the third of laminated film Alkenyl body mixes, and the extrusion coating paper of the laminated film containing stalk fibre has been made, and the laminated film not only has good tensile strength, Also there is good gas permeability, be highly suitable for preparing the packaging material of fruits and vegetables.
In a kind of preferred embodiment of the present invention, in order to further improve obtained stalk fibre laminated film Tensile strength and gas permeability, the stalk of crushing, water, the mass ratio of TEMPO and hypochlorite are 20:50-100：5-7：3-4.
In a kind of preferred embodiment of the present invention, in order to further improve obtained stalk fibre laminated film Tensile strength and gas permeability, the stalk of crushing, water, the mass ratio of TEMPO and hypochlorite are 20:50-100：5-7：3-4.
In a kind of preferred embodiment of the present invention, in order to further improve obtained stalk fibre laminated film Tensile strength and gas permeability, the condition of oxidation processes include：PH is 12-14, and processing time 1-2h, temperature is 40-70 DEG C.
In a kind of preferred embodiment of the present invention, in order to further improve obtained stalk fibre laminated film Tensile strength and gas permeability, in step (2), the condition of mixing includes：Temperature is 50-70 DEG C, time 20-30min.
In a kind of preferred embodiment of the present invention, in order to further improve obtained stalk fibre laminated film Tensile strength and gas permeability, the condition of softening include：Temperature is 80-95 DEG C, time 15-25min.
In a kind of preferred embodiment of the present invention, in order to further improve obtained stalk fibre laminated film Tensile strength and gas permeability, in step (3), the condition of precompressed includes：Pressure is 2.5-3.5MPa, and temperature is 140-160 DEG C.
In a kind of preferred embodiment of the present invention, in order to further improve obtained stalk fibre laminated film Tensile strength and gas permeability, the condition of hot pressing include：Pressure is 40-60MPa, and temperature is 170-190 DEG C.
In a kind of preferred embodiment of the present invention, in order to further improve obtained stalk fibre laminated film Tensile strength and gas permeability, the condition of sanding comprise at least：The time of sanding is 20-30min.
In a kind of preferred embodiment of the present invention, in order to further improve obtained stalk fibre laminated film Tensile strength and gas permeability, in parts by weight, dried oxidation stalk 40-50 parts, polyacrylate 10-20 parts, You Jirong Agent 15-25 parts, polypropylene 60-80 parts, citric acid 8-10 parts, sodium dihydrogen phosphate 6-8 parts, Tissuemat E 3-5 parts, HBB 8-10 Part and ethylene glycol 3-5 parts.
In a kind of preferred embodiment of the present invention, in order to further improve obtained stalk fibre laminated film Tensile strength and gas permeability, wherein, the weight average molecular weight of polyacrylate is 5000-7000, the weight average molecular weight of Tissuemat E For 7000-8000, polyacrylic weight average molecular weight is 10000-30000.
In a kind of preferred embodiment of the present invention, in order to further improve obtained stalk fibre laminated film Tensile strength and gas permeability, stalk in wheat stalk, broomcorn straw, cotton stalk, maize straw and rice straw one Kind is a variety of.
In a kind of preferred embodiment of the present invention, in order to further improve obtained stalk fibre laminated film Tensile strength and gas permeability, in step (1), the length of the stalk after crushing is not more than 2cm.
In a kind of preferred embodiment of the present invention, in order to further improve obtained stalk fibre laminated film Tensile strength and gas permeability, hypochlorite are the one or more in postassium hypochlorite, sodium hypochlorite and calcium hypochlorite.
In a kind of preferred embodiment of the present invention, in order to further improve obtained stalk fibre laminated film Tensile strength and gas permeability, organic solvent are the one or more in methanol, ethanol, tetrahydrofuran, ethylene glycol, glycerine.
In the above-mentioned technical solutions, paper layer can be selected in relative broad range, in order that film layer is in paper layer knot Conjunction property is preferable, it is preferable that paper layer is brown paper or corrugated paper.
Present invention also offers a kind of extrusion coating paper of laminated film containing stalk fibre, the laminated film containing stalk fibre Extrusion coating paper is made by above-mentioned preparation method.The laminated film not only has good tensile strength, also has good breathe freely Property, film heat and hot pressing is in being made Film laminated paper on the surface of paper layer, is highly suitable for preparing the bag of fruits and vegetables Package material.
The present invention will be described in detail by way of examples below.In following examples, polyacrylate is divided equally again Son amount is 5000-7000, and the weight average molecular weight of Tissuemat E is 7000-8000；Polyacrylic weight average molecular weight is 10000- 30000。
Following tensile strength parameter is measured by GB1040-2006 method；OTR oxygen transmission rate (unit mL/m2, My god, standard atmospheric pressure) test is measured using the OTR oxygen transmission rate tester of model 8001, and corresponding standard is GB/ T1038-2000 plastic sheetings and thin slice gas-premeable test method；Moisture-vapor transmission (unit mL/m2) test use The water vapor permeation rate testers of model Model 3/33 are detected, and corresponding standard is GB/T 30412-2013 plastic sheetings With the measure of thin slice moisture-vapor transmission.
Preparation example 1
In parts by weight, 20 parts of stalks are crushed into (length of the stalk after crushing is not more than 2cm), is scattered in 50 parts of water In, add TEMPO 5 parts of (2,2,6,6- tetramethyl -1- piperidines-N- epoxides), 3 parts of hypochlorite carry out oxidation processes (pH 12, Processing time is 2h, and temperature is 70 DEG C), wherein, it is used as pH adjusting agent by the use of sodium hydroxide, drying after oxidation processes.
Preparation example 2
In parts by weight, 20 parts of stalks are crushed into (length of the stalk after crushing is not more than 2cm), is scattered in 100 parts of water In, add TEMPO 7 parts of (2,2,6,6- tetramethyl -1- piperidines-N- epoxides), 4 parts of hypochlorite carry out oxidation processes (pH 14, Processing time is 1h, and temperature is 40 DEG C), wherein, it is used as pH adjusting agent by the use of sodium hydroxide, drying after oxidation processes.
Preparation example 3
In parts by weight, 20 parts of stalks are crushed into (length of the stalk after crushing is not more than 2cm), is scattered in 75 parts of water In, add TEMPO 6 parts of (2,2,6,6- tetramethyl -1- piperidines-N- epoxides), 3.5 parts of hypochlorite carries out oxidation processes (pH is 13, processing time 1.5h, temperature are 55 DEG C), wherein, pH adjusting agent is used as by the use of sodium hydroxide, drying after oxidation processes.
Preparation example 4
In parts by weight, 20 parts of stalks are crushed into (length of the stalk after crushing is not more than 2cm), is scattered in 75 parts of water In, add TEMPO 10 parts of (2,2,6,6- tetramethyl -1- piperidines-N- epoxides), 10 parts of hypochlorite carries out oxidation processes (pH is 13, processing time 1.5h, temperature are 55 DEG C), wherein, pH adjusting agent is used as by the use of sodium hydroxide, drying after oxidation processes.
Preparation example 5
In parts by weight, 20 parts of stalks are crushed into (length of the stalk after crushing is not more than 2cm), is scattered in 75 parts of water In, add TEMPO 3 parts of (2,2,6,6- tetramethyl -1- piperidines-N- epoxides), 2 parts of hypochlorite carry out oxidation processes (pH 13, Processing time is 1.5h, and temperature is 55 DEG C), wherein, it is used as pH adjusting agent by the use of sodium hydroxide, drying after oxidation processes.
Embodiment 1
In parts by weight, 40 parts of the dried oxidation stalk that will be prepared in preparation example 1,10 parts of polyacrylate and ethanol 15 parts carry out mixing 30min in 70 DEG C, carry out softening 25min after 95 DEG C, obtain stalk mixture；Then polypropylene is added 60 parts, 8 parts of citric acid, 6 parts of sodium dihydrogen phosphate, 3 parts of Tissuemat E, the 3 parts of mixing of 8 parts of HBB and ethylene glycol, then carry out pre- Pressure, preload pressure 3.5MPa, temperature are 160 DEG C, are then 60MPa in pressure, temperature carries out heat under conditions of being 190 DEG C Pressure, last sanding 30min, film is made；Film heat and 180 DEG C of hot pressing are on the surface of paper layer.
The tensile strength of obtained stalk fibre laminated film is 17.4MPa, OTR oxygen transmission rate 1775mL/m2, water steaming Vapor permeability is 6.4mL/m2。
Embodiment 2
In parts by weight, 50 parts of the dried oxidation stalk that will be prepared in preparation example 2,20 parts of polyacrylate and ethanol 25 parts carry out mixing 20min in 50 DEG C, carry out softening 15min after 80 DEG C, obtain stalk mixture；Then polypropylene is added 80 parts, 10 parts of citric acid, 8 parts of sodium dihydrogen phosphate, 5 parts of Tissuemat E, the 5 parts of mixing of 10 parts of HBB and ethylene glycol, then carry out Precompressed, preload pressure 2.5MPa, temperature are 140 DEG C, are then 40MPa in pressure, temperature carries out heat under conditions of being 170 DEG C Pressure, last sanding 20min, film is made；Film heat and 180 DEG C of hot pressing are on the surface of paper layer.
The tensile strength of obtained stalk fibre laminated film is 17.9MPa, OTR oxygen transmission rate 1820mL/m2, water steaming Vapor permeability is 6.7mL/m2。
Embodiment 3
In parts by weight, 45 parts of the dried oxidation stalk that will be prepared in preparation example 3,15 parts of polyacrylate and ethanol 20 parts carry out mixing 25min in 60 DEG C, carry out softening 20min after 88 DEG C, obtain stalk mixture；Then polypropylene is added 70 parts, 9 parts of citric acid, 7 parts of sodium dihydrogen phosphate, 4 parts of Tissuemat E, the 4 parts of mixing of 9 parts of HBB and ethylene glycol, then carry out pre- Pressure, preload pressure 3MPa, temperature are 150 DEG C, are then 50MPa in pressure, and temperature carries out hot pressing under conditions of being 180 DEG C, Last sanding 25min, is made film；Film heat and 180 DEG C of hot pressing are on the surface of paper layer.Obtained stalk is fine The tensile strength for tieing up laminated film is 18.5MPa, OTR oxygen transmission rate 1844mL/m2, moisture-vapor transmission 6.8mL/m2。
Embodiment 4
The extrusion coating paper of the laminated film containing stalk fibre is prepared according to the preparation method in embodiment 3, unlike, it will prepare The dried oxidation stalk prepared in example 3 is changed to " the dried oxidation stalk prepared in preparation example 4 ".Obtained stalk The tensile strength of fiber composite film is 18.1MPa, OTR oxygen transmission rate 1615mL/m2, moisture-vapor transmission 5.8mL/m2。
Embodiment 5
The extrusion coating paper of the laminated film containing stalk fibre is prepared according to the preparation method in embodiment 3, unlike, it will prepare The dried oxidation stalk prepared in example 3 is changed to " the dried oxidation stalk prepared in preparation example 5 ".It is obtained to contain straw The tensile strength of the extrusion coating paper of stalk fiber laminated film is 16.8MPa, OTR oxygen transmission rate 1726mL/m2, moisture-vapor transmission For 5.4mL/m2。
Embodiment 6
The extrusion coating paper of the laminated film containing stalk fibre is prepared according to the preparation method in embodiment 3, unlike, precompressed, The condition of hot pressing and sanding is：Preload pressure is 2MPa, and temperature is 160 DEG C, and then pressure is 30MPa, and temperature is 190 DEG C of bar Hot pressing and sanding 30min are carried out under part.The tensile strength of obtained stalk fibre laminated film is 17.1MPa, OTR oxygen transmission rate For 1745mL/m2, moisture-vapor transmission 8.2mL/m2。
Embodiment 7
The extrusion coating paper of the laminated film containing stalk fibre is prepared according to the preparation method in embodiment 3, unlike, soften bar Part is：Temperature is 100 DEG C and carries out softening 30min.The tensile strength of obtained stalk fibre laminated film is 17.6MPa, oxygen Transmitance is 1723mL/m2, moisture-vapor transmission 8.3mL/m2。
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should equally be considered as content disclosed in this invention.

Claims (10)

1. the preparation method of the extrusion coating paper of a kind of laminated film containing stalk fibre, it is characterised in that the preparation method includes：
(1) stalk is crushed, be dispersed in water, deposited in TEMPO (2,2,6,6- tetramethyl -1- piperidines-N- epoxides), hypochlorite Oxidation processes are carried out in case, are dried；
(2) dried oxidation stalk, polyacrylate and organic solvent are mixed, is softened afterwards, obtain stalk Mixture；
(3) stalk mixture, polypropylene, citric acid, sodium dihydrogen phosphate, Tissuemat E, HBB and ethylene glycol are mixed, then Precompressed, hot pressing and sanding are carried out, film is made；
(4) film heat and hot pressing is on the surface of paper layer.
2. preparation method according to claim 1, wherein, the stalk of crushing, water, TEMPO and hypochlorite quality it Than for 20：50-100：5-7：3-4.
3. preparation method according to claim 2, wherein, the condition of oxidation processes includes：PH is 12-14, processing time For 1-2h, temperature is 40-70 DEG C.
4. preparation method according to claim 1, wherein, in step (2), the condition of mixing includes：Temperature is 50-70 DEG C, time 20-30min；And/or
The condition of softening includes：Temperature is 80-95 DEG C, time 15-25min.
5. preparation method according to claim 1, wherein, in step (3), the condition of precompressed includes：Pressure is 2.5- 3.5MPa, temperature are 140-160 DEG C.
6. preparation method according to claim 1, wherein, the condition of hot pressing includes：Pressure is 40-60MPa, and temperature is 170-190℃；
And/or the condition of sanding comprises at least：The time of sanding is 20-30min.
7. preparation method according to claim 1, wherein, in parts by weight, dried oxidation stalk 40-50 parts, gather Acrylate 10-20 parts, organic solvent 15-25 parts, polypropylene 60-80 parts, citric acid 8-10 parts, sodium dihydrogen phosphate 6-8 parts, gather Ethylene waxes 3-5 parts, HBB 8-10 parts and ethylene glycol 3-5 parts.
8. preparation method according to claim 7, wherein, the weight average molecular weight of polyacrylate is 5000-7000, poly- second The weight average molecular weight of alkene wax is 7000-8000, and polyacrylic weight average molecular weight is 10000-30000.
9. preparation method according to claim 1, wherein, stalk is selected from wheat stalk, broomcorn straw, cotton stalk, jade One or more in rice stalk and rice straw；
And/or in step (1), the length of the stalk after crushing is not more than 2cm；
And/or hypochlorite is the one or more in postassium hypochlorite, sodium hypochlorite and calcium hypochlorite；
And/or organic solvent is the one or more in methanol, ethanol, tetrahydrofuran, ethylene glycol, glycerine；
And/or paper layer is brown paper or corrugated paper.
10. the THIN COMPOSITE containing stalk fibre that the preparation method in a kind of 1-9 according to claim described in any one is prepared The extrusion coating paper of film.
CN201711142841.6A 2017-11-17 2017-11-17 Extrusion coating paper of the laminated film containing stalk fibre and preparation method thereof Pending CN107826462A (en)

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